1,2,5,6-tetrahydropyridyl triazoles and tetrazoles useful as fungicides

ABSTRACT

Compounds of the formula (I): ##STR1## and stereoisomers and salts thereof, wherein R 1  and R 2 , are optionally substituted alkyl; V is either oxygen or sulphur; Y is hydrogen, optionally substituted alkyl, cyano, nitro or halogen; X is ##STR2## Z is NOR 5  or ##STR3## A is CO 2  R 6 , COR 7 , cyano, nitro or acylamino; B is hydrogen, optionally substituted alkyl, optionally substituted aryl, CO 2  R 8 , COR 9 , cyano, nitro or acylamino, or A and B together form a ring containing one or more heteroatoms; R 4  is CO 2  R 3  or R 17  ; R 12  is OR 13 , SR 14 , NR 15  R 16  or R 18  ; R 3  is optionally substituted alkyl;and R 5  to R 11  and R 13  to R 18 , which are the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aralkyl, optionally substituted aryl, or optionally substituted heteroaryl, or R 10  and R 11 , or R 15  and R 16  together with their adjacent nitrogen atom join to form a saturated ring (except that R 10  and R 11 , together with their adjacent nitrogen atom, do not form an unsubstituted piperidine ring when R 1  and R 2  are both methyl, Y is hydrogen and V is oxygen) optionally containing one or more hetero atoms in addition to the nitrogen atom, for example, a pyrrolidine or morpholine. These compounds are useful in agriculture, for example, as fungicides or plant growth regulators.

This invention relates to derivatives of acrylic acid useful inagriculture (especially as fungicides but also as plant growthregulators, insecticides, nematocides and miticides), to processes forpreparing them, to agricultural (especially fungicidal) compositionscontaining them, and to methods of using them to combat fungi(especially fungal infections in plants), to regulate plant growth andto control or kill insects, nematodes and mites.

The invention provides a compound having the general formula (I):##STR4## and stereoisomers and salts thereof, wherein R¹ and R², whichare the same or different, are optionally substituted alkyl (preferablymethyl); V is either oxygen or sulphur; Y is hydrogen, optionallysubstituted alkyl, cyano, nitro or halogen (fluorine, chlorine, bromine,or iodine); X is ##STR5## Z is NOR⁵ or A is CO₂ R⁶, COR⁷, cyano, nitroor acylamino; B is hydrogen, optionally substituted alkyl, optionallysubstituted aryl, CO₂ R⁸, COR⁹, cyano, nitro or acylamino, or A and Btogether form a ring containing one or more heteroatoms; R⁴ is CO₂ R³ orR¹⁷ ; R¹² is OR¹³, SR¹⁴, NR¹⁵ R¹⁶ or R¹⁸ ; R³ is optionally substitutedalkyl; and R⁵ to R¹¹ and R¹³ to R¹⁸, which are the same or different,are hydrogen, optionally substituted alkyl, optionally substitutedcycloalkyl, optionally substituted cycloalkylalkyl, optionallysubstituted alkenyl, optionally substituted alkynyl, optionallysubstituted aralkyl, optionally substituted aryl, or optionallysubstituted heteroaryl, or R¹⁰ and R¹¹, or R¹⁵ and R¹⁶ together withtheir adjacent nitrogen atom join to form a saturated ring (except thatR¹⁰ and R¹¹, together with their adjacent nitrogen atom, do not form anunsubstituted piperidine ring when R¹ and R² are both methyl, Y ishydrogen and V is oxygen) optionally containing one or more hetero atomsin addition to the nitrogen atom, for example, a pyrrolidine ormorpholine ring.

The compounds of the invention contain at least one carbon-carbon doublebond and are sometimes obtained as mixtures of geometric isomers.However, these mixtures can be separated into individual isomers, andthis invention embraces such isomers and mixtures thereof in allproportions including those which consist substantially of the(E)-isomer and those which consist substantially of the (Z)-isomer.

The individual isomers which result from the unsymmetrically substituteddouble bond of the acrylate group are identified by the commonly usedterms "E" and "Z". These terms are defined according to theCahn-Ingold-Prelog system which is fully described in the literature(see, for example, J March, "Advanced Organic Chemistry", 3rd edition,Wiley-Interscience, page 109 et seq).

Usually one isomer is more fungicidally active than the other; the moreactive isomer being the one in which the group -VR² is on the same sideof the double bond as the pyrrole ring. In the case of the compounds ofthe present invention this is the (Z)-isomer. The (Z)-isomers form apreferred embodiment of the invention.

The formula: ##STR6## used herein indicates that the compound may be inthe form of one or both isomers, i.e. ##STR7##

Compounds in which X is CH₂ NR¹⁰ R¹¹ can form acid addition salts, forexample hydrochloride salts and hydrosulphate salts. They can also formquaternary ammonium salts, for example the methiodide salt or the benzylhalide (e.g. bromide) quaternary ammonium salt.

Preferred alkyl groups contain from 1 to 6, especially 1 to 4, carbonatoms and can be in the form of straight or branched chains; theyinclude methyl, ethyl, propyl (n- and iso-propyl) and butyl (n-, sec-,iso-, and tert-butyl).

It is preferred that R¹ and R² are both methyl.

Preferred cycloalkyl groups are those containing from 3 to 6 carbonatoms, i.e. cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.Preferred cycloalkylalkyl groups are those containing from 3 to 8,especially 3 to 6, carbon atoms in the alkyl ring and 1 to 6, especially1 to 4, carbon atoms in the attached alkyl chain. Examples arecyclopropylethyl and cyclohexylmethyl.

Optional substituents of alkyl, cycloalkyl and cycloalkylalkyl includehydroxy, halogen (especially chlorine and fluorine), C₁₋₄ alkoxy andC₁₋₄ alkoxycarbonyl.

A preferred aryl group is phenyl which may be unsubstituted orsubstituted with, for example, 1, 2 or 3 substituents at the 2-, 3- or4-positions of the ring. Optional substituents carried by the aryl groupinclude halogen (especially chlorine or fluorine), hydroxy, alkyl,trifluoromethyl, and trifluoromethoxy and may be the same or different.Examples of optionally substituted aryl groups are phenyl, 2-, 3- or4-chlorophenyl, 2,4- or 3,5-dichlorophenyl, 2,4- or 3,5-difluorophenyl,2-, 3- or 4-fluorophenyl, 2-, 3- or 4-methoxyphenyl,2,4-dimethoxyphenyl, 2-fluoro-4-chlorophenyl, 2-, 3- or 4-methylphenyland 2-, 3- or 4-trifluoromethylphenyl.

Aralkyl includes, particularly, phenyl(C₁₋₄)alkyl (especially benzyl,phenylethyl and phenylpropyl) and the aryl moiety may be substituted inthe same way as the aryl groups above.

Alkenyl and alkynyl groups preferably contain 2 to 6, more preferably 2to 4, carbon atoms in the form of straight or branched chains. Allyl andpropargyl are examples. Optional substituents of alkenyl and alkynylinclude aromatic and heteroaromatic groups (such as phenyl, furyl,thienyl and pyridyl) which may themselves be substituted in the same wayas the aryl groups above.

Heteroaryl includes pyridyl, pyrimidinyl, thiophenyl, furyl and pyrroyl.Optional substituents include those described for the aryl groups above.

In one particular aspect, the invention provides compounds having theformula (Ia): ##STR8## and stereoisomers thereof, wherein Y is hydrogen,optionally substituted alkyl, cyano, nitro or halogen; R⁴ is hydrogen,optionally substituted alkyl, or optionally substituted aryl; Z is NOR⁵or ##STR9## R⁵ is hydrogen, optionally substituted alkyl, optionallysubstituted alkenyl, optionally substituted alkynyl, optionallysubstituted aralkyl, optionally substituted aryl, or optionallysubstituted heteroaryl; A is CO₂ R⁶, COR⁷, cyano, nitro, or acylamino; Bis hydrogen, optionally substituted alkyl, optionally substituted aryl,CO₂ R⁸, COR⁹, cyano, nitro or acylamino, or A and B together form a ringcontaining one or more heteroatoms; and R⁶, R⁷, R⁸ and R⁹, which are thesame or different, are optionally substituted alkyl, optionallysubstituted cycloalkyl, optionally substituted cycloalkylalkyl,optionally substituted alkenyl, optionally substituted alkynyl,optionally substituted aralkyl, optionally substituted aryl, oroptionally substituted heteroaryl. Preferred alkyl, alkenyl, alkynyl,aralkyl, aryl and heteroaryl groups and their optional substituents arethe same as those described above.

The invention is illustrated by the compounds listed in Tables I to IIIwhich follow.

NMR data for selected compounds are given in Table IV.

                                      TABLE I                                     __________________________________________________________________________     ##STR10##                                                                    COMPOUND                                                                      NO.      R.sup.1                                                                          R.sup.2                                                                          R.sup.4                                                                             V  Y  Z          Mpt. °C.                                                                    OLEFINIC*                                                                            ISOMER.sup.+                                                                        ISOMER°        __________________________________________________________________________    1        CH.sub.3                                                                         CH.sub.                                                                          H     O  H  NOCH.sub.3 Oil  7.57    --Z   --E                  2        CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  NOCH.sub.3 Oil  7.60    --Z   --Z                  3        CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  NOCH.sub.2 CHCH.sub.2                                                                    Oil  7.50    --Z   --E                  4        CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  NOCH.sub.2 CHCH.sub.2                                                                    Oil  7.68    --Z   --Z                  5        CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  NOCH.sub.2 C.sub.6 H.sub.5                                                               Oil  7.44    --Z   --E                  6        CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  NOCH.sub.2 C.sub.6 H.sub.5                                                                            --Z   --Z                  7        CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  NOCH.sub.2 CCH                                                                           Oil  7.53    --Z   --E                  8        CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  NOCH.sub.2 CCH          --Z   --Z                  9        CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                            O  H  NOCH.sub.3              --Z   --E                  10       CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                            O  H  NOCH.sub.3              --Z   --Z                  11       CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  CHCO.sub.2 CH.sub.3                                                                      Oil  7.70    --Z   --E                  12       CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  CHCO.sub.2 C.sub.2 H.sub.5                                                               Oil  7.68    --Z   --E                  13       CH.sub. 3                                                                        CH.sub.3                                                                         H     O  H  NOH                     --Z   --E                  14       CH.sub.3                                                                         CH.sub.3                                                                         C.sub.6 H.sub.5                                                                     O  H  NOCH.sub.3              --Z   --E                  15       CH.sub.3                                                                         CH.sub.3                                                                         C.sub.6 H.sub.5                                                                     O  H  NOH                     --Z   --E                  16       CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                            O  H  NOC.sub.6 H.sub.5       --Z   --E                  17       CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                            O  H  NO(3-FC.sub.6 H.sub.4)  --Z   --E                  18       CH.sub.3                                                                         CH.sub.3                                                                         CO.sub.2 CH.sub.3                                                                   O  H  NOCH.sub.3              --Z   --E                  19       CH.sub.3                                                                         CH.sub.3                                                                         H     O  H                                                                                 ##STR11## 121-2                                                                              7.76    --Z   --E                  20       CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  CHCOCH.sub.3            --Z   -- E                 21       CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  CHCOC.sub.6 H.sub.5     --Z   --E                  22       CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  C(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                                   --Z   --E                  23       CH.sub.3                                                                         CH.sub.3                                                                         H     O  H  C(CH.sub.3)NO.sub.2     --Z   --E                  24       CH.sub.3                                                                         CH.sub.3                                                                         H     O  CH.sub.3                                                                         NOCH.sub.2 CHCH.sub.2   --Z   --E                  __________________________________________________________________________     *Chemical shift of singlet from olefinic proton on the betaalkoxyacrylate     or beta(alkylthio)acrylate group (ppm from tetramethylsilane).                Solvent:CDCl.sub.3.                                                           .sup.+ Geometry of betaalkoxyacrylate or beta(alkylthio)acrylate group.       °Geometry of oxime, oxime ether, or olefin, at the 2position of th     pyrrole.                                                                 

                                      TABLE II                                    __________________________________________________________________________     ##STR12##                                                                    COMPOUND                                             QUATERNARY               NO.      R.sup.1                                                                          R.sup.2                                                                          V Y  R.sup.10                                                                            R.sup.11                                                                            Mpt. °C.                                                                      OLEFINIC*                                                                             ISOMER.sup.+                                                                        SALT                     __________________________________________________________________________    1        CH.sub.3                                                                         CH.sub.3                                                                         O H  CH.sub.3                                                                            CH.sub.3                                                                            54-6   7.47     --Z  --                       2        CH.sub.3                                                                         CH.sub.3                                                                         O H  CH.sub.3                                                                            CH.sub.3                                                                            ca.300 8.01     --Z  METHIODIDE                                               DECOMP.              SALT                     3        CH.sub.3                                                                         CH.sub.3                                                                         O H  H     C.sub.6 H.sub.5       --Z  --                       4        CH.sub.3                                                                         CH.sub.3                                                                         O H  H      .sub.-n-C.sub.3 H.sub.7                                                                            --Z  --                       5        CH.sub.3                                                                         CH.sub.3                                                                          O                                                                              H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                      Oil    7.54     --Z  --                       6        CH.sub.3                                                                         CH.sub.3                                                                         O H  CH.sub.3                                                                            C.sub.6 H.sub.5       --Z  --                       7        CH.sub.3                                                                         CH.sub.3                                                                         O CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3              --Z  --                       8        CH.sub.3                                                                         CH.sub.3                                                                         O H  C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5       --Z  --                       __________________________________________________________________________     *Chemical shift of singlet from olefinic proton on the betaalkoxyacrylate     or beta(alkylthio)acrylate group (ppm from tetramethylsilane).                Solvent:CDCl.sub.3.                                                           .sup.+ Geometry of betaalkoxyacrylate or beta(alkylthio)acrylate group.  

                                      TABLE III                                   __________________________________________________________________________     ##STR13##                                                                    COMPOUND                                                                      NO.     R.sup.1                                                                          R.sup.2                                                                          V Y R.sup.12    Mpt. °C.                                                                    OLEFINIC*                                                                            ISOMER.sup.+                        __________________________________________________________________________    1       CH.sub.3                                                                         CH.sub.3                                                                         O H C.sub.6 H.sub.5          --Z                                2       CH.sub.3                                                                         CH.sub.3                                                                         O H 4-ClC.sub.6 H.sub.4      --Z                                3       CH.sub.3                                                                         CH.sub.3                                                                         O H 3-ClC.sub.6 H.sub.4      --Z                                4       CH.sub.3                                                                         CH.sub.3                                                                         O H 4-FC.sub.6 H.sub.4       --Z                                5       CH.sub.3                                                                         CH.sub.3                                                                         O H 2-FC.sub.6 H.sub.4       --Z                                6       CH.sub.3                                                                         CH.sub.3                                                                         O H 3-CH.sub.3C.sub.6 H.sub.4                                                                              --Z                                7       CH.sub.3                                                                         CH.sub.3                                                                         O H 3-CH.sub.3 OC.sub.6 H.sub.4                                                                            --Z                                8       CH.sub.3                                                                         CH.sub.3                                                                         O H 3,5-DiFC.sub.6 H.sub.3   --Z                                9       CH.sub.3                                                                         CH.sub.3                                                                         O H 3,5-DiCH.sub.3C.sub.6 H.sub.3                                                                          --Z                                10      CH.sub.3                                                                         CH.sub.3                                                                         O H 3,5-DiClC.sub.6 H.sub.3  --Z                                11      CH.sub.3                                                                         CH.sub.3                                                                         O H O( .sub.-n-C.sub.3 H.sub.7)                                                                            --Z                                12      CH.sub.3                                                                         CH.sub.3                                                                         O H OC.sub.6 H.sub.5         --Z                                13      CH.sub.3                                                                         CH.sub.3                                                                         O H O( .sub.-n-C.sub.4 H.sub.9)                                                                            --Z                                14      CH.sub.3                                                                         CH.sub.3                                                                         O H (NHCH.sub.3)             --Z                                15      CH.sub.3                                                                         CH.sub.3                                                                         O H N(CH.sub.3).sub.2        --Z                                16      CH.sub.3                                                                         CH.sub.3                                                                         O H NHC.sub.6 H.sub.5        --Z                                17      CH.sub.3                                                                         CH.sub.3                                                                         O H N(CH.sub.3)C.sub.6 H.sub.5                                                                             --Z                                18      CH.sub. 3                                                                        CH.sub.3                                                                         O H SCH.sub.3                --Z                                19      CH.sub.3                                                                         CH.sub.3                                                                         O H SC.sub.6 H.sub.5         --Z                                20      CH.sub.3                                                                         CH.sub.3                                                                         O H NHCO.sub.2 C.sub.2 H.sub.5                                                                             --Z                                21      CH.sub.3                                                                         CH.sub.3                                                                         O H NH(3-FC.sub.6 H.sub.4)   --Z                                22      CH.sub.3                                                                         CH.sub.3                                                                         O H NH(4-ClC.sub.6 H.sub.4)  --Z                                __________________________________________________________________________     *Chemical shift of singlet from olefinic proton on the betaalkoxyacrylate     or beta(alkylthio)acrylate group (ppm from tetramethylsilane).                Solvent:CDCl.sub.3.                                                           .sup.+ Geometry of betaalkoxyacrylate or beta(alkylthio)acrylate group.  

                  TABLE IV                                                        ______________________________________                                        Selected proton NMR data                                                      Table IV shows selected proton NMR data for certain                           compounds described in Tables I and II. Chemical shifts                       are measured in ppm from tetramethylsilane, and                               deuterochloroform was used as solvent throughout. The                         following abbreviations are used:                                             br   = broad   t = triplet ppm  =   parts per million                         s    = singlet q = quartet J    =   coupling constant                         d    = doublet m = multiplet        in hertz (Hz)                             ______________________________________                                        COM-                                                                          POUND   TABLE                                                                 NO.     NO.       NMR DATA                                                    ______________________________________                                        1       I         3.75 (3) s, 3.87 (3) s, 3.89 (3) s, 6.3                                       (1) m, 6.6 (2) m, 7.57 (1) s, 7.88 (1)                                        s.                                                          2       I         3.64 (3) s, 3.80 (3) s, 3.90 (3) s, 6.3                                       (1) m, 6.5 (1) m, 6.90 (1) s, 7.1 (1) m,                                      7.60 (1) s.                                                 3       I         3.70 (3) s, 3.84 (3) s, 4.5 (2) m, 5.1-5.4                                    (2) m, 5.8-6.7 (4) m, 7.50 (1) s, 7.88 (1)                                    s.                                                          4       I         3.72 (3) s, 3.88 (3) s, 4.7 (2) m, 5.1-6.7                                    (5) m, 7.03 (1) s, 7.3 (1) m, 7.68 (1) s.                   5       I         3.64 (3) s, 3.72 (3) s, 5.06 (2) s, 6.2-                                      6.7 (3) m, 7.2-7.4 (5) m, 7.44 (1) s, 7.92                                    (1) s.                                                      7       I         3.73 (3) s, 3.88 (3) s, 4.64 (2) s, 6.3-                                      6.7 (3) m, 7.53 (1) s, 7.90 (1) s.                           11     I         3.76 (6) s, 3.90 (3) s, 6.1 (1) d                                             (J = 16Hz), 6.4 (1) m, 6.8 (2) m, 7.4 (1) d                                   (J = 16Hz), 7.70 (1) s.                                      12     I         1.3 (3) t, 3.75 (3) s, 3.86 (3) s, 4.2 (2)                                    q, 6.1 (1) d (J = 16Hz), 6.2-6.8 (3) m, 7.3                                   (1) d (J = 16Hz), 7.68 (1) s.                                19     I         3.75 (3) s, 3.81 (3) s, 6.46 (1) m, 6.76                                      (1) m, 7.06 (1) s, 7.2-7.6 (6) m, 7.76                                        (1) s.                                                      1        II       2.08 (6) s, 3.16 (2) s, 3.64 (3) s, 3.80                                      (3) s, 6.0-6.2 (2) m, 6.4-6.5 (1) m, 7.47                                     (1) s.                                                      2        II       3.00 (6) s, 3.78 (3) s, 3.96 (3) s, 4.30                                      (2) s, 6.4 (1) m, 6.6 (1) m, 6.8 (1) m,                                       8.01 (1) s.                                                 5        II       2.2-2.4 (4) m, 3.3 (2) m, 3.5-3.6 (4) m,                                      3.73 (3) s, 3.86 (3) s, 6.1 (1) m, 6.17                                       (1) m, 6.53 (1) m, 7.54 (1) s.                              ______________________________________                                    

The compounds of the invention having the general formula (I), in whichV is oxygen, can be prepared by the steps shown in Schemes I to III.Throughout the Schemes the terms A, B, R¹ to R¹⁸, X, Y and Z are asdefined above and L is a leaving group such as a halide (iodide, bromideor, especially, chloride) or --R² SO₄ anion.

Referring to Scheme I, compounds of the invention having the generalformula (I) wherein X is ##STR14## and Z is NOR⁵ [compound (IA) ofScheme I] may be prepared from substituted pyrroles of general formula(II) by treatment with amines of general formula H₂ NOR⁵ in a suitablesolvent such as methanol.

Compounds of the general formula (I) wherein X is ##STR15## and Z is CAB[compound (IB) of Scheme I] may be prepared from substituted pyrroles ofgeneral formula (II) by treatment with a Wittig reagent of generalformula (C₆ H₅)₃ P:CAB, (see, for example, "The Chemistry of Pyrroles",Academic Press, R. A. Jones, G. P. Bean, page 316, and referencestherein). Alternatively, when one or both of the groups A and Bstabilise an adjacent negative charge, compounds (IB) of Scheme I may beprepared by condensation of substituted pyrroles of general formula (II)with compounds of general formula CH₂ AB. They may also be prepared byreaction of compounds of general formula (III) of Scheme I withcompounds of general formula R⁴ C═C--A, optionally in the presence of aLewis acid; in this case the group B of the product (1B) is hydrogen(see, for example, "Advances in Heterocyclic Chemistry", Academic Press,1978, 23, 286 and references therein).

Compounds of general formula (I) wherein X is ##STR16## [compound (IC)of Scheme I] may be prepared by catalytic hydrogenation (preferablyusing a palladium catalyst) of compounds of general formula (IB) ofScheme I. Alternatively, they may be prepared from substituted pyrrolesof general formula (III) by treatment with compounds of general formula##STR17## optionally in the presence of a Lewis acid (see D. O. Cheng,T. L. Bowman and E. LeGoff, Journal of Heterocyclic Chemistry, 1976, 13,1145).

Compounds of the general formula (I) wherein X is CH₂ NR¹⁰ R¹¹ [compound(ID) of Scheme I] may be prepared from substituted pyrroles of generalformula (III) of Scheme I by treatment with an amine of general formulaHNR¹⁰ R¹¹ and formaldehyde using a Mannich reaction (see W. Hertz and J.L. Rogers, J. Amer. Chem. Soc., 1951, 73, 4921). ##STR18##

Compounds of the general formula (II) of Scheme I may be prepared fromsubstituted pyrroles of general formula (III) by treatment with aVilsmeier reagent, and subsequent quenching with an aqueous base. TheVilsmeier reagent may, for example, be prepared by adding phosphorylchloride to an amide of general formula (CH₃)₂ NCOR⁴ (see for example,Organic Synthesis, John Wiley and Sons, Inc., Collective Volume 4, page831, and references therein).

Referring to Scheme II, compounds of the general formula (I) wherein Xis ##STR19## [Compound (IE) of Scheme II] may be prepared fromsubstituted pyrroles of general formula (III), by treatment with acompound of general formula ##STR20## optionally in the presence of aLewis acid catalyst.

Alternatively, when R¹² is NHR¹⁵, they may be prepared by treatment ofsubstituted pyrroles of general formula (III) with an isothiocyanate ofgeneral formula R¹⁵ --NCS, optionally in the presence of a Lewis acidcatalyst (see, for example, V Looney-Dean, B. S. Lindamood and E. P.Papadopoulos, Synthesis, 1984, 68 and references therein). Compounds offormula (IE) wherein R¹² is R¹⁸ may be prepared via the Vilsmeiercomplex of general formula (IV); treatment of substituted pyrroles ofgeneral formula (III) with an amide of general formula (CH₃)₂ NCOR¹⁸ inphosphoryl chloride generates a Vilsmeier complex which is then quenchedwith the group ⁻ SH, to give the thioaroylpyrroles of general formula(IE) [see, for example, T. Anderson, M. Phil. Thesis, University of EastAnglia, 1971]. ##STR21##

Alternatively, if compounds of general formula (III) are treated withthiophosgene (CSCl₂) the intermediate of general formula (V) isobtained; this may then be transformed into compounds of general formula(IE) by methods known in the chemical literature. Examples includetreatment with amines of general formula HNR¹⁵ R¹⁶, or alcohols ofgeneral formula HOR¹³ to give compounds where R¹² is the group NR¹⁵ R¹⁶and OR¹³ respectively (see for example, P. S. Clezy, G. A. Smythe,Australian Journal of Chem., 1969, 22, 239).

Referring to Scheme III, compounds of general formula (III) can beprepared by treatment of substituted acetic esters of general formula(VII) of Scheme III with a base and a formic ester HCO₂ R¹, such asmethyl formate, in a suitable solvent and quenching the reaction with asuitable species of general formula R² L.

Alternatively, compounds of general formula (VI) may be isolated byquenching the reaction with acid. In such cases, conversion intocompounds of general formula (III) can be performed in a separate stepby successive treatments with a suitable base (such as sodium carbonateor potassium carbonate) and a suitable reagent of general formula R² Lin a suitable solvent. Alternatively, alkali metal salts of compounds ofgeneral formula (VI) may be isolated and converted into compounds ofgeneral formula (III) by treatment with a suitable reagent of generalformula R² L in a suitable solvent, as a subsequent step. Compounds ofgeneral formula (VII) can be prepared by treatment of pyrroles ofgeneral formula (VIII) with a suitable base, such as sodium hydride orpotassium tert-butoxide, and a substituted acetic ester of generalformula LCH₂ CO₂ R¹, in a suitable solvent.

Alternatively, compounds of general formula (VII) may be prepared bytreatment of the appropriately substituted dialkoxytetrahydrofuran ofgeneral formula (IX) with the glycine ester of general formula H₂ NCH₂CO₂ R¹ in a suitable solvent, for example, acetic acid, (see C. W.Jefford and W. Johncock, Helvetica Chimica Acta, 1983, 66, 2666).##STR22##

Furthermore, compounds of general formula (III) can be made from acetalsof general formula (X) under either basic or acidic conditions, insuitable solvents and at suitable temperatures. An example of a suitablebase is lithium di-isopropylamide, and potassium hydrogen sulphate is anexample of a suitable acidic reagent (see T. Yamada, H. Hagiwara and H.Uda, Journal of the Chem. Soc., Chem. Commun. 1980, 838, and referencestherein).

Acetals of general formula (X) may be prepared from pyrroleacetic estersof general formula (VII) by treatment of alkyl silyl ketene acetalderivatives of species (VII) with trialkylorthoformates of generalformula (R² O)₃ CH in the presence of a Lewis acid in a suitable solventand at a suitable temperature (see, for example, K. Saigo, M. Osaki andT. Mukaiyama, Chem. Letts., 1976, 769).

Compounds of general formula (I) in which V is sulphur may be obtainedfrom thioethers corresponding to ethers of general formula (III),wherein OR² is replaced by SR², using the various processes shown inSchemes I and II. Thioethers corresponding to ethers of general formula(III), wherein OR² is replaced by SR², may be obtained by treatingcompounds of general formula (VI) with a suitable reagent of generalformula R¹⁹ SO₂ Cl, wherein R¹⁹ is alkyl or optionally substituted aryl,in a suitable solvent and often in the presence of a base and thenquenching with a reagent of general formula NaSR², wherein R² is definedabove, e.g. sodium methanethiolate.

Moreover, compounds of formulae (IA), (IB), (IC), (ID) or (IE) may,where appropriate, be prepared from the appropriately substitutedpyrrole of general formula (XI): ##STR23## via compounds of generalformulae (XII), (XIII) and (XIV): ##STR24## using the sequence outlinedbefore in Scheme III to convert compounds of general formula (VIII) tocompounds of general formula (III).

Compounds of general formulae (VIII), (IX) and (XI) may be prepared bymethods known in the chemical literature.

In further aspects, the invention provides processes as herein describedfor preparing the compounds of the invention and the intermediatechemicals of formulae (IV), (V), (X) and (XII) to (XIV) used therein.

The compounds of the invention are active fungicides and may be used tocontrol one or more of the following pathogens:

Pyricularia oryzae on rice.

Puccinia recondita, Puccinia striiformis and other rusts on wheat,Puccinia hordei, Puccinia striiformis and other rusts on barley, andrusts on other hosts e.g. coffee, pears, apples, peanuts, vegetables andornamental plants. Erysiphe graminis (powdery mildew) on barley andwheat and other powdery mildews on various hosts such as Sphaerothecamacularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber),Podosphaera leucotricha on apple and Uncinula necator on vines.Helminthosporium spp., Rhynchosporium spp., and Septoria spp. oncereals. Cercospora arachidicola and Cercosporidium personata on peanutsand other Cercospora species on other hosts for example sugar beet,bananas, soya beans and rice. Botrytis cinerea (grey mould) on tomatoes,strawberries, vegetables, vines and other hosts. Alternaria species onvegetables (e.g. cucumber), oil-seed rape, apples, tomatoes and otherhosts. Venturia inaequalis (scab) on apples. Plasmopara viticola onvines. Other downy mildews such as Bremia lactucae on lettuce,Peronospora spp. on soybeans, tobacco, onions and other hosts andPseudoperonospora humuli on hops and Pseudoperonospora cubensis oncucurbits.

Phytophthora infestans on potatoes and tomatoes and other Phytophthoraspp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco,cocoa and other hosts.

Some of the compounds show a broad range of activities against fungi invitro. They may also have activity against various post-harvest diseasesof fruit (e.g. Penicillium digitatum and italicum and Trichoderma virideon oranges, Gloeosporium musarum on bananas and Botrytis cinerea ongrapes).

Further some of the compounds may be active as seed dressings againstFusarium spp., Septoria spp., Tilletia spp., (bunt, a seed-borne diseaseof wheat), Ustilago spp. and Helminthosporium spp. on cereals andPyricularia oryzae on rice.

The compounds may move acropetally in the plant tissue.

The invention therefore provides a method of combating fungi, whichcomprises applying to a plant, to a seed of a plant, or to the locus ofthe plant or seed, a fungicidally effective amount of a compound ashereinbefore defined, or a composition containing the same.

The compounds may also be useful as industrial (as opposed toagricultural) fungicides, e.g. in the prevention of fungal attack onwood, hides, leather and especially paint films.

Some of the compounds exhibit insecticidal activity and, at appropriaterates of application, may be used to combat a range of insect, nematodeand mite pests.

Therefore in another aspect of the invention there is provided a methodof killing or controlling insect, nematode and mite pests whichcomprises administering to the pest or to the locus thereof aninsecticidally, nematocidally or miticidally effective amount ofcompound as hereinbefore defined or a composition containing the same.

Preferred compounds for use in this method are those of formula (II) inwhich Z is NOR⁵ or C(A)B; R⁴, Y and B are hydrogen; A is C₁₋₄alkoxycarbonylmethyl; and R⁵ is C₁₋₆ alkyl, C₂₋₆ alkenyl or C₂₋₆alkynyl, and especially compounds 2, 3, 7 and 11 of Table I.Particularly preferred compounds for killing nematode pests are those offormula (II) in which Z is NOR⁵ ; R⁴, Y and B are hydrogen and R⁵ isC₂₋₆ alkenyl, and especially compound 3 of Table I.

Some compounds exhibit plant growth regulating activity and may bedeployed for this purpose, again at appropriate rates of application.

Therefore, in yet another aspect the invention provides a method ofregulating plant growth which comprises applying to a plant, to a seedof a plant or to the locus of the plant or seed an effective amount of acompound as hereindefined or a composition containing the same.Preferred compounds for use in this method are those of formula (II).

The compounds may be used directly for agricultural purposes but aremore conveniently formulated into compositions using a carrier ordiluent. The invention thus provides fungicidal, plant growth regulator,insecticidal, nematicidal and miticidal compositions comprising acompound as hereinbefore defined, and an acceptable carrier or diluenttherefor.

The compounds can be applied in a number of ways. For example they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted, or they can be sprayed on, dusted on or applied as a creamor paste formulation, or they can be applied as a vapour or as slowrelease granules. Application can be to any part of the plant includingthe foliage, stems, branches or roots, or to soil surrounding the roots,or to the seed before it is planted; or to the soil generally, to paddywater or to hydroponic culture systems. The invention compounds may alsobe injected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatment.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example fillers such as kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,Fuller's earth, gypsum, diatomaceous earth and China clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler. Compositions for dressingseed may include an agent (for example a mineral oil) for assisting theadhesion of the composition to the seed; alternatively the activeingredient can be formulated for seed dressing purposes using an organicsolvent (for example N-methylpyrrolidone, propylene glycol orN,N-dimethylformamide). The compositions may also be in the form ofwettable powders or water dispersible granules comprising wetting ordispersing agents to facilitate the dispersion in liquids. The powdersand granules may also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a wetting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as isophorone, cyclohexanone, and methylcyclohexanone, chlorinatedhydrocarbons such as chlorobenzene and trichlorethane, and alcohols suchas benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent and including a suspendingagent to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure in the presence ofa propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in microencapsulated form. Theymay also be formulated in biodegradable polymeric formulations to obtaina slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for examplecetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), and salts of sulphonated aromatic compounds (for examplesodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonite orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having similar or complementaryfungicidal activity or which plant possess plant growth regulating,herbicidal or insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear diseases ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil-borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple etc. By including anotherfungicide, the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further the other fungicidecan have a synergistic effect on the fungicidal activity of the compoundof general formula (I). Examples of fungicidal compounds which may beincluded in the composition of the invention are carbendazim, benomyl,thiophanate-methyl, thiabendazole, fuberidazole, etridazole,dichlofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl,benalaxyl, fosetyl-aluminium, fenarimol, iprodione, prothiocarb,procymidone, vinclozolin, penconazole, myclobutanil, propamocarb,R0151297, diniconazole, pyrazophos, ethirimol, ditalimfos, tridemorph,triforine, nuarimol, triazbutyl, guazatine, triacetate salt of1,1'-iminodi(octamethylene)diguanidine, buthiobate, propiconazole,prochloraz, flutriafol, hexaconazole, (2 RS, 3RS)-2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol,(RS)-1-(4-cholorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol,fluzilazole, triadimefon, triadimenol, diclobutrazol, fenpropimorph,pyrifenox, fenpropidin, chlorozolinate, imazalil, fenfuram, carboxin,oxycarboxin, methfuroxam, dodemorph, BAS 454, blasticidin S,kasugamycin, edifenphos, Kitazin P, cycloheximide, phthalide,probenazole, isoprothiolane, tricyclazole,4-chloro-N-(cyano(ethoxy)methyl)benzamide, pyroquilon,chlorbenzthiazone, neoasozin, polyoxin D, validamycin A, mepronil,flutolanil, pencycuron, diclomezine, phenazin oxide, nickeldimethyldithiocarbamate, techlofthalam, bitertanol, bupirimate,etaconazole, hydroxyisoxazole, streptomycin, cyprofuram, biloxazol,quinomethionate, dimethirimol, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea, fenapanil, tolclofos-methyl, pyroxyfur, polyram, maneb, mancozeb,captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb,propineb, sulphur, dinocap, dichlone, chloroneb, binapacryl,nitrothal-isopropyl, dodine, dithianon, fentin hydroxide, fentinacetate, tecnazene, quintozene, dicloran, copper containing compoundssuch as copper oxychloride, copper sulphate and Bordeaux mixture, andorganomercury compounds. The compounds of general formula (I) can bemixed with soil, peat or other rooting media for the protection ofplants against seed-borne, soil-borne or foliar fungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include pirimicarb, dimethoate, demeton-s-methyl,formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan,diazinon, fenthion, fenitrothion, phenthoate, chlorpyrifos, isoxathion,propaphos, monocrotophas, buprofezin, ethroproxyfen and cycloprothrin.

Plant growth regulating compounds are compounds which control weeds orseedhead formation, or selectively control the growth of less desirableplants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compounds are the gibberellins (e.g. GA₃, GA₄ or GA₇), theauxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acidor naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea,benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoicacid), morphactins (e.g. chlorfluoroecol), maleic hydrazide, glyphosate,glyphosine, long chain fatty alcohols and acids, dikegulac,paclobutrazol, fluoridamid, mefluidide, substituted quaternary ammoniumand phosphonium compounds (e.g. chloromequat chlorphonium ormepiquatchloride), ethephon, carbetamide, methyl-3,6-dichloroanisate,daminozide, asulam, abscisic acid, isopyrimol,1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, hydroxybenzonitriles (e.g. bromoxynil), difenzoquat,benzoylprop-ethyl 3,6-dichloropicolinic acid, fenpentezol, inabenfide,triapenthenol and tecnazene.

The following Examples illustrate the invention. Throughout theseexamples, magnesium sulphate was used to dry solutions. Solutions wereconcentrated under reduced pressure, and reactions involving watersensitive intermediates were performed under an atmosphere of nitrogen.HPLC is high performance liquid chromatography; DMF isN,N-dimethylformamide; m.p. is melting point. Percentages are by weight.

EXAMPLE 1

This Example illustrates the preparation of the 2 geometric isomers of(Z)-methyl 3-methoxy-2-[2-(N-methoxyimino)pyrrol-1-yl]acrylate:Compounds 1 and 2 of Table 1.

A solution of the hydrochloride salt of the methyl ester of glycine(6.30 g) and potassium acetate (8.00 g) in water (10 ml) was added toglacial acetic acid (50 ml). The resulting mixture was heated to reflux,2,5-dimethoxytetrahydrofuran (6.60 g) was added in one portion, andheating under reflux was continued for 4 hours. After cooling, thereaction mixture was neutralised with sodium bicarbonate and extractedwith ethyl acetate. The extracts were washed with water, dried,concentrated under reduced pressure, and distilled at 125° C. and ca. 15torr using a short-path distillation apparatus to give methylpyrrol-1-ylacetate (2.62 g, 38% yield) as a colourless liquid, infrared(film) 1750 cm⁻¹.

A solution of methyl pyrrol-1-ylacetate (2.00 g) in methyl formate (4.4ml) was added dropwise to a stirred suspension of sodium hydride (0.38g) in dry toluene (10 ml) cooled in an ice bath. The mixture was allowedto warm to room temperature, 2 drops of dry methanol were added(effervescence), and it was heated slowly to 50° C. whereupon themixture became at first clear, then deposited a thick off-white solid.The mixture was heated at 50° C. for 30 minutes, allowed to cool anddiluted with ether. The solid was filtered off, washed with ether andpartially dried to give a white solid (3.12 g) infrared (film) 1665,1650 cm⁻¹. Methyl iodide (0.93 ml) was added in one portion to a stirredsuspension of this solid in DMF (20 ml). After stirring at roomtemperature for 2 hours, the mixture was poured into water and extractedwith ether. The extracts were washed with water, dried and concentratedto give a white solid (2.35 g) which was triturated with petrol anddried to give (Z)-methyl 3-methoxy-2-(pyrrol-1-yl)acrylate (1.73 g, 66%)as a white solid, m.p. 88°-9° C., infrared (nujol-mull) 1700, 1635 cm⁻¹,proton n.m.r. (CDCl₃) delta: 3.77 (3) s, 3.91 (3) s, 6.26 (2) t, 6.69(2) t, 7.51 (1) s.

A solution of (Z)-methyl 3-methoxy-2-(pyrrol-1-yl)acrylate (10 g, 0.055mol) in 1,2-dichloroethane (25 ml) was added dropwise with stirring atroom temperature to the mixture resulting from adding phosphorylchloride (5.6 ml, 0.06 mol) to DMF (4.7 ml, 0.06 mol) while cooling inice. After stirring for 3 hours at room temperature, a saturated aqueoussolution of sodium acetate (100 ml) was added and the resulting mixturewas heated at reflux for 30 minutes. The mixture was cooled thenextracted with dichloromethane (2×150 ml). The extracts were washed withwater, dried and concentrated to give a clear oil (11.7 g, of a mixtureof the 2 and 3-formylated pyrrole) which was purified by HPLC on silicagel using diethyl ether as the eluant to give (Z)-methyl3-methoxy-2-(2-formylpyrrol-1-yl)acrylate (5.7 g, 45%) as a whitecrystalline solid, m.p. 58°-9° C., proton n.m.r. (CDCl₃) delta: 3.74 (3)s, 3.88 (3) s, 6.35 (1) m, 6.87 (1) m, 7.04 (1) m, 7.55 (1) s, 9.30 (1)d.

A mixture of the (Z)-methyl 3-methoxy-2-(2-formylpyrrol-1-yl)acrylate(0.5 g, 0.0024 mol), anhydrous sodium acetate (1.0 g, 0.012 mol) andmethoxylamine hydrochloride (0.5 g, 0.006 mol) was refluxed in methanolfor 3 hours. The resulting mixture was concentrated and the residue waspartitioned between ethyl acetate (100 ml) and water (100 ml). The ethylacetate layer was washed with brine, dried, concentrated and purified byHPLC on a column of silica gel using ether as the eluant to give:

(i) a clear oil (0.33 g, 57%), the (E)-isomer of the title compound(Compound 1 of Table I), which eluted first and,

(ii) a clear oil (0.24 g, 42%) the (Z)-isomer of the title compound(Compound 2 of Table I), which eluted second.

EXAMPLE 2

This Example illustrates, with reference to Scheme IV, the preparationof (Z)-methyl 3-methoxy-2-[2-(E-2-carbethoxyethenyl)pyrrol-1-yl]acrylate(XII; Scheme IV): Compound 12 of Table I.

Referring to Scheme IV, a mixture of (Z)-methyl3-methoxy-2-(2-formylpyrrol-1-yl)acrylate [1.0 g, 0.005 mol, (XIII);Scheme IV: preparation described in Example 1] and ethyl(triphenylphosphoranylidene)acetate (1.74 g, 0.005 mol) was refluxed indry toluene (40 ml) for 30 hours. After cooling, the solution wasconcentrated and the residue was extracted with diethyl ether. Theseextracts were concentrated and then purified by HPLC on a column ofsilica gel using diethyl ether as the eluant, to give the title compoundas a light orange oil (0.65 g, 47%). ##STR25##

EXAMPLE 3

This Example illustrates the preparation of (Z)-methyl3-methoxy-2-[2-(dimethylaminomethyl)pyrrol-1-yl]acrylate: Compound 1 ofTable II.

Dimethylamine (5.4 g of a 33% aqueous solution, 0.04 mol) was added,with stirring, to glacial acetic acid (5 ml) whilst cooling in an icebath; after 15 minutes formalin (3 mls of a 40% aqueous solution, 0.04mol) was added and the mixture was stirred for 1 hour. (Z)-methyl3-methoxy-2-(pyrrol-1-yl)acrylate (3.6 g, 0.02 mol, prepared asdescribed in Example 1) was added and the mixture was stirred overnight.This was then concentrated and the residue was dissolved in water (100ml). The resulting aqueous solution was washed with ether, neutralisedwith sodium bicarbonate, then extracted with ethyl acetate (2×80 ml).The extracts were dried and concentrated to give the title compound(3.75 g, 79%) as an oil which solidified on trituration with petrol60°-80° C.; m.p. 54°-56° C.

EXAMPLE 4

This Example illustrates the preparation of the quaternary methiodidesalt of (Z)-methyl3-methoxy-2-[2-(dimethylaminomethyl)pyrrol-1-yl]acrylate: Compound 2 ofTable II.

Iodomethane (0.53 ml, 0.0085 mol) was added to a solution of (Z)-methyl3-methoxy-2-[2-(dimethylaminomethyl)pyrrol-1-yl]acrylate (1.9 g, 0.008mol, prepared as described in Example 3) in chloroform (20 ml). Thissolution was kept at 0° C. for 16 hours, then concentrated and theresidue was washed with ether to give the title compound (2.5 g, 85%) asa white crystalline solid, which did not melt on heating, but insteaddarkened at ca. 300° C.

EXAMPLE 5

An emulsifiable concentrate is made up by mixing and stirring theingredients until all are dissolved.

    ______________________________________                                        Compound No. 1 (Table II)                                                                            10%                                                    Benzyl alcohol         30%                                                    Calcium dodecylbenzenesulphonate                                                                      5%                                                    Nonylphenolethoxylate (13 moles                                                                      10%                                                    ethylene oxide)                                                               Alkyl benzenes         45%                                                    ______________________________________                                    

EXAMPLE 6

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed onto granules of attapulgite clay. The solventis then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No. 1 (Table II)                                                                           5%                                                      Attapulgite granules 95%                                                      ______________________________________                                    

EXAMPLE 7

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No. 1 (Table II)                                                                          50%                                                      Mineral oil           2%                                                      China clay           48%                                                      ______________________________________                                    

EXAMPLE 8

A dustable powder is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No. 1 (Table II)                                                                           5%                                                      Talc                 95%                                                      ______________________________________                                    

EXAMPLE 9

A suspension concentrate is prepared by ball milling the ingredients toform an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No. 1 (Table II)                                                                          40%                                                      Sodium lignosulphonate                                                                             10%                                                      Bentonite clay        1%                                                      Water                49%                                                      ______________________________________                                    

This formulation can be used as a spray by diluting into water orapplied directly to seed.

EXAMPLE 10

A wettable powder formulation is made by mixing then grinding theingredients until all thoroughly mixed.

    ______________________________________                                        Compound No. 1 (Table II)                                                                          25%                                                      Sodium lauryl sulphate                                                                              2%                                                      Sodium lignosulphonate                                                                              5%                                                      Silica               25%                                                      China clay           43%                                                      ______________________________________                                    

EXAMPLE 11

This Example illustrates the fungicidal properties of compounds 1 to 5,7, 11, 12 and 19 of Table I and 5 of Table II when tested against avariety of foliar fungal diseases of plants. The technique employed wasas follows.

The plants were grown in John Innes Potting Compost (No. 1 or 2) in 4 cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formulations (100ppm active ingredient) were sprayed on to the foliage and applied to theroots of the plants in the soil. The sprays were applied to maximumretention and the root drenches to a final concentration equivalent toapproximately 40 ppm a.i./dry soil. Tween 20, to give a finalconcentration of 0.05%, was added when the sprays were applied tocereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.Foliar pathogens were applied by spray as spore suspensions onto theleaves of test plants. After inoculation, the plants were put into anappropriate environment to allow infection to proceed and then incubateduntil the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3=trace - 5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Table V.

                                      TABLE V                                     __________________________________________________________________________                                   PYRIC-         PLASMO-                         COM-    PUCCINIA                                                                              ERYSIPHE                                                                             VENTURIA                                                                              ULARIA                                                                             CERCOSPCRA                                                                              PARA   PHYTOPHTHORA             POUND                                                                             TA- RECONDITA                                                                             GRAMINIS                                                                             INAEQUALIS                                                                            ORYZAE                                                                             ARACHIDICOLA                                                                            VITICOLA                                                                             INFESTANS                NO. BLE (Wheat) (Barley)                                                                             (Apple) (Rice)                                                                             (Peanut)  (Vine) (TOMATOES)               __________________________________________________________________________    1   I   4       4      4       4    4         4      3                        2   I   4       4      4       3    4         4      0                        3   I   4       4      4       --   4         4      0                        4   I   4       4      4       4    4         4      4                        5   I   3       3      4       4    3         4      0                        7   I   4       4      4       4    4         4      3                        11  I   4       4      4       4    2         4      4                        12  I   4       0      4       4    4         4      4                        19  I   4       0      0       0    3         4      0                        5   II  2       2      4       0    4         0      0                        __________________________________________________________________________

EXAMPLE 12

This Example illustrates the plant growth regulating properties ofcompounds 1 to 5, 7, 11 and 12 of Table I when tested on a whole plantscreen against various plant species. The plant species are identifiedin Table VI with the leaf stage at which they were sprayed.

A formulation of each chemical was applied at 4000 ppm (4 kg/ha in a1000 1/ha field volume) using a tracksprayer and a SS8004E (Teejet)nozzle.

After spraying, the plants were grown in a glasshouse with 25° C.day/22° C. night temperatures. Supplementary lighting was supplied whennecessary to provide an average photoperiod of 16 hours (14 hoursminimum).

After 2-6 weeks in the glasshouse, depending on species and time ofyear, the plants were visually assessed for morphologicalcharacteristics against a control plant sprayed with a blankformulation. The results are presented in Table VII.

                                      TABLE VI                                    __________________________________________________________________________    PLANT MATERIAL USED FOR WHOLE PLANT SCREEN                                                      Growth Stage                                                                           No Plants                                                                           Compost                                      Species                                                                             Code                                                                             Variety  at Treatment                                                                           per 3" pot                                                                          Type                                         __________________________________________________________________________    Barley                                                                              BR Atem     1-1.5 leaves                                                                           4     JIP*                                         Maize MZ Earliking                                                                              21/4-21/2 leaves                                                                       1     PEAT                                         Apple AP Red Delicious                                                                          4-5 leaves                                                                             1     JIP                                          Rice  RC Ishikari 2-21/2 leaves                                                                          4     JIP                                          Tomato                                                                              TO Ailsa Craig                                                                            2-21/2 leaves                                                                          1     PEAT                                         __________________________________________________________________________     *John Innes Potting Compost                                              

                  TABLE VII                                                       ______________________________________                                        Plant  Compound                                                               Material                                                                             No.         R      G    A    T    I    P                               ______________________________________                                        BR     3                                                                      BR     4                                                                      BR     5                                                                      BR      11                                    1                               RC     3                            1                                         RC     4                  1                                                   RC     5                                                                      RC      11         1                     1                                    AP     3                                                                      AP     4           2                     2                                    AP     5           2                     2                                    AP      11         1                     1                                    TO     3           3           3              3                               TO     5           3           3              3                               TO     7           2           3    2    2    2                               TO      11         3           3    1         3                               TO      12         3           3         3    3                               MZ     1           1                     2                                    MZ     2                                                                      MZ     3           1           3                                              MZ     4                       1                                              MZ     5                                                                      MZ     7           1                                                          MZ      11         1                                                          MZ      12         2      1              3                                    ______________________________________                                         KEY                                                                           R = Retardation                                                               G = Greening effect                                                           A = Apical damage                                                              T = Tillering or side shooting                                               I = Interligular of internodal length reduction                               P = Phytotoxicity                                                             All effects, except phytotoxicity, are scored visually on a 1-3 basis         where                                                                         1 = 10-30%                                                                    2 = 31-60%                                                                    3 = 61-100%                                                                   Blank means less than 10% effect.                                             Phytotoxicity is scored on a 1-5 basis where                                  1 = less than 10%                                                             2 = 11-30%                                                                    3 = 31-50%                                                                    4 = 51-70%                                                                    5 = greater than 70%                                                          Blank means no effect at all observed.                                   

EXAMPLE 13

This Example illustrates the insecticidal properties of compounds 2, 3,7 and 11 of Table I.

The activity of the compounds was determined using a variety of insect,mite and nematode pests. The compounds were used in the form of liquidpreparations containing 500 parts per million (ppm) by weight of thecompound except for the test on Meloidogyne incognita when liquidpreparations of 250 ppm by weight were used. The preparations were madeby dissolving the compounds in acetone and diluting the solutions withwater containing 0.1% by weight of a wetting agent sold under the tradename "SYNPERONIC" NX until the liquid preparations contained therequired concentration of the product. "SYNPERONIC" is a RegisteredTrade Mark.

The test procedure adopted with regard to each pest was basically thesame and comprised supporting a number of the pests on a medium whichwas usually a host plant or a foodstuff on which the pests feed, andtreating either or both the pests and the medium with the preparations.The mortality of the pests was then assessed at periods usually varyingfrom one to seven days after the treatment.

The results of the tests are given in Table IX for each of the productsas a grading of mortality designated as 9, 5 or 0 where 9 indicates80-100% mortality (70-100% root-knot reduction as compared withuntreated plants for Meloidogyne incognita), 5 indicates 50-79%mortality (50-69% root knot reduction for Meloidogyne incognita) and 0indicates less than 50% mortality (root-knot reduction for Meloidogyneincognita).

In Table IX the pest organism used in designated by a letter code andthe pests species, the support medium or food, and the type and durationof test is given in Table VII.

                  TABLE VII                                                       ______________________________________                                        CODE                                                                          LETTERS              SUPPORT    TYPE                                          (Table               MEDIUM/    OF                                            IV)   TEST SPECIES   FOOD       PEST   DAY                                    ______________________________________                                        TUa   Tetranychus urticae                                                                          French bean                                                                              Contact                                                                              3                                            (spider mites - adult)                                                                       leaf                                                     TUe   Tetranyhus urticae                                                                           French bean                                                                              Contact                                                                              6                                            (spider mites - ova)                                                                         leaf                                                     MP    Myzus persicae Chinese    Contact                                                                              3                                            (aphids)       Cabbage leaf                                             NL    Nilaparvata lugens                                                                           Rice plant Contact                                                                              3                                            (brown plant hopper -                                                         nymphs)                                                                 HV    Heliothis virescens                                                                          Cotton leaf                                                                              Residual                                                                             3                                            (tobacco budworm -                                                            larvae)                                                                 DB    Diabrotica balteata                                                                          Filter paper/                                                                            Residual                                                                             3                                            (rootworm larvae)                                                                            maize seed                                               BG    Blattella germanica                                                                          Plastic pot                                                                              Residual                                                                             3                                            (cockroach nymphs)                                                      MD    Musca domestica                                                                              Cotton wool/                                                                             Contact                                                                              1                                            (houseflies - adults)                                                                        sugar                                                    SP    Spodoptera exigua                                                                            Cotton leaf                                                                              Residual                                                                             3                                            (lesser army worm -                                                           larvae)                                                                 MI    Meloidogyne incognita                                                                        Semi in-vitro                                                                            Residual                                                                             7                                            (tomato root knot                                                             eelworm - larvae)                                                       NC    Nephotettix cincticeps                                                                       Rice plant Contact                                                                              3                                            (green leaf hopper -                                                          nymph)                                                                  ______________________________________                                    

                                      TABLE VII                                   __________________________________________________________________________    COMPOUND                                                                      NO.     TU.sub.a                                                                         TU.sub.e                                                                         MP NL MD BG HV SP DB MI NC                                      __________________________________________________________________________    2       9  0  9  0  0  0  0  0  5  0  --                                      3       9  0  0  9  9  9  0  0  9  5  --                                      7       9  0  0  0  0  5  -- -- 9  0  --                                      11      9  0  0  -- 0  9  0  -- 0  0  5                                       __________________________________________________________________________

The knockdown properties of compound 3 in Table I against Muscadomestica were demonstrated as follows.

A sample of compound 3 was diluted in 2 mls acetone and made upto a 2000ppm solution with 0.1% aqueous synperonic solution. The solution (1 ml)was then sprayed directly onto twenty mixed sex houseflies held in adrinking cup. Immediately after spraying the cups were inverted and leftto dry. An assessment of knockdown was made when the cups were righted15 minutes later. The flies were then provided with a 10% sucrosesolution on a cotton wool pad, and held for 48 hours in a holding roomconditioned at 25° C. and 65% relative humidity before a mortalityassessment was made.

Compound 3 in Table I under these conditions demonstrated 90% knockdownand 93% kill.

We claim:
 1. A compound of formula (I): ##STR26## and stereoisomers andsalts thereof, wherein R¹ and R², which are the same or different, areC₁₋₆ alkyl; V is oxygen or sulphur; Y is hydrogen, C₁₋₆ alkyl, cyano,nitro or halogen; X is ##STR27## Z is NOR⁵ or ##STR28## A is CO₂ R⁶,COR⁷, cyano, nitro or acylamino; B is hydrogen, C₁₋₆ alkyl, phenyl, CO₂R⁸, COR⁹, cyano, nitro or acylamino; R⁴ is CO₂ R³ or R¹⁷ ; R³ is C₁₋₆alkyl; R⁵ to R⁹ and R¹⁷, which are the same or different, are hydrogen,C₁₋₆ alkyl, C₃₋₆ cycloalkyl, C₃₋₈ cycloalkyl-(C₁₋₆)alkyl, C₂₋₆ alkenyl,C₂₋₆ alkynyl, phenyl or phenyl(C₁₋₆)alkyl; any alkyl, cycloalkyl orcycloalkylalkyl moiety being unsubstituted or substituted with hydroxy,halogen, C₁₋₄ alkoxy or C₁₋₄ alkoxycarbonyl, any alkynyl or alkenylmoeity being unsubstituted or substituted with phenyl, and any phenylbeing unsubstituted or substituted with halogen, hydroxy, C₁₋₆ alkyl,methoxy, trifluoromethyl or trifluoromethoxy.
 2. A fungicidalcomposition comprising as an active ingredient a compound according toclaim 1 and a fungicidally acceptable carrier or diluent therefor.
 3. Amethod of combating fungi which comprises applying to a plant, to seedof a plant or to the locus of the plant or seed, a compound according toclaim
 1. 4. A compound according to claim 1 wherein R¹ and R² aremethyl, V is oxygen, R⁴ is hydrogen, C₁₋₆ alkyl or phenyl and R⁵ ishydrogen, C₁₋₆ alkyl, C₂₋₆ alkynyl, C₂₋₆ alkynyl, phenyl orphenyl(C₁₋₄)alkyl.